Bacteria inhibited lubricant composition



United States Patent 3,257,320 BACTERIA INHIBITED LUBRICANT COMPOSITION Edward B. Hodge, Terre Haute, Ind., assignor to Commercial Solvents Corporation, a corporation of Maryland No Drawing. Filed Oct. 14, 1963, Ser. No. 316,133

7 Claims. (Cl. 252-515) The present application is a continuation-in-part application of my copending US. Patent application, Serial No. 157,274, filed December 5, 1961, now U.S. Patent No. 3,160,634, and entitled, Novel Compositions of Matter.

The present invention relates to novel petroleum lubricant compositions, and more particularly to petroleum lubricants containing, as an active inhibitor against bacteria action, a 1,3-bis[3-(oxazolidinyl)]prop ane having the following formula wherein R is a lower alkyl, hydrogen, or lower hydroxyalkyl, and R is lower-alkyl.

It is well known that organisms from the groups consisting of Corynebacterium, Achromobacter, Pseudomonas, Nocardia and Mycobacterium metabolize petroleum hydrocarbons and fatty acids and thereby produce undesirable oxidation products.

Frequently, for example, the presence of bacteria, such as anaerobic and aerobic bacteria, deleteriously affects emulsifying and, when present, corrosion inhibiting components of soluble oils such as those used as cutting, spraying and rust preventing oils. These oils generally include a base lubricating oil, a small amount of water, and an emulsifying agent as well as optional additive-s, e.g., corrosion inhibitors. The components in soluble oils are employed in amounts to provide a stable emulsion or dispersion when the soluble oil is incorporated into relatively large proportionate amounts of water for use as a lubricant and. coolant in metal cutting and machining operations. The deleterious effects of the bacteria in soluble oils include reduction of sulfonate emulsifiers, oxidation of nitrogen-containing emulsifiers or corrosion inhibitors and the reduction of inorganic sulfates present in waters mixed with the soluble oils.

The petroleum industry has long been interested in the inhibition of bacterial'and fungicidal action in various petroleum products such as soluble oils. Many compounds have been used as bacteria inhibitors, but very few have been found to be of commercial value due to the fact that the compounds are unstable, insoluble, or are not active against a wide variety of microorganisms.

It is an object of the present invention, therefore, to provide novel petroleum lubricants, especially petroleum lubricants containing improved bacteria inhibitors to combat the deleterious effects of bacteria in petroleum lubriice can't, e.g. soluble oil, compositions. It is a further object of the present invention to produce novel petroleum lubricants, such as soluble oil compositions, containing bacteria inhibiting amounts of a l,3-bis[3-(ox-azolidinyl)1 propane having the general formula:

wherein R is selected from the group consisting of lower alkyl, lower hydroxyalkyl, and hydrogen and R is lower alkyl. Qther objects of the present invention will become apparent from the detailed description hereinbelow.

Among. the 1,3-bis[3-(oxazolidinyl) ]propanes having the above structured formula are, for example,

2-nitro 2 methyl 1,3-bis[3-(4,4-dimethy1oxazolidinyl)] propane,

2-nitro 2-ethy1 1,3-bis[3-(4,4-dimethyloxazolidinyl)] propane, v

2-nitro 2-methyl-l,3-bis[3-(4,4-dihyd-roxymethyloxazolidinyl) propane,

2-nitro-2-rnethyl-1,3-bis[3-(oxazolidinyl) ]propane,

2-nitro 2 methyl 1,3-bis[3-(4-propyloxazolidinyl)]propane,

Z-nitro Z-methyl 1,3-bis[3-(5 methyloxazolidinyl)]propane,

etc., and the like. The present invention is based on the discovery that. such 1,3-bis[3-(oxazolidinyl)Jpropanes,

especially when used in pe troleum containing lubricants such as cutting oils, grinding lubricants, core oils, penetrating oils, hydraulic fluids, iron tinning lubricants, etc.,

exhibit bacteria inhibiting characteristics.

The 1,3- bis[3-(oxaz-o1idinyl)]propanes of the present invention are usually employed in conventional bacteriainhibiting amounts, generally from about 0.1 to 10 weight per-cent, preferably from about 0.5 to 5 weight percent, based on the oil.

The 1,3-bis[3-(oxazolidinyl)]propanes may be produced according to the process of my copending patent application referred to above by a condensation reaction which consists of heating a mixture of formaldehyde, lower nitroalkane and oxazolidine to form the 1,3-bis-[3- 3 (oxazolidinyl)]propane with accompanying liberation of water.

Generally, in preparing the 1,3-bis[3-(oxazolidinyl)] propanes, it is preferred to utilize the theoretical amounts of reactants. Thus, for every mole of nitroalkane it is preferred to utilize 2 moles of formaldehyde and 2 moles of oxazolidine although this ratio is not required. In carrying out the reaction, it is also generally preferred, although it is not absolutely necessary, that a solvent, such as water or the lower alcohols, be used and that the excess solvent and product water be removed after formation of the 1,3-bis[3-(oxazol iclinyl) lpropane by simple distillation.

The starting oxazolidines which are utilized in the production" of the l,3-bis[3-(oxazolidinyl) propane are those having the following general formula:

wherein R is lower alkyl, hydrogen, or lower hydroxyalkyl. Such oxazolidin'es include 4,4-dimethyloxazolidine, 4,4-diethyloxazolidine, 4,4-dihydroxymethyloxazolidine, 4- propyloxazolidine, S-methyloxazolidine, oxazolidine, etc., andthe like. Such oxazolidines are readily available and are easily prepared by condensing an amino alcohol having at least one hydroxyl group on the carbon atom adjacent to the carbon atom to which the amine group is attached with a lower aldehyde in the presence of an inert hydrocarbon solvent such as benzene, toluene, xylene, etc. Included among the amino alcohols which can be utilized in preparing the oxazolidines used in my reaction are 2-amino-2-methyl-l propanol, tris(hydroxymethyl) aminomethane, ethanolamine, isopropanolamine, etc., and the like.

As stated previously, petroleum lubricants such as soluble oil compositions generally include a lubricating base oil, an emulsifying agent and a small amount of water, e.g., from about 0.1 to 10 percent. The types and proportions of the various ingredients used in compositions of this character are quite flexible and may be varied according to the particular properties desired in the finished product. The oils used as a base in the compositions of the present invention, which are conventionally prepared, are those 5 usually used in soluble oils and include the refined mineral lubricating oils, for instance, a conventionally treated (steam refined), substantially anhydrous pale oil with a viscosity for instance within the range from about to 1200 S.U.S. at 100 F., usually not up to about 500 S.U.S. at 100 F. l

The emulsifiers are generally the surface active agents conventionally employed in soluble oils and will normally comprise from about 1 to 50, frequently about 2 to 20, weight percent of the soluble oil. They include the petroleum sulfonates described in US Patent No. 2,516,838 as well as the products of reacting an alkylene oxide with phenolic material as described in US. Patent No. 2,692; 859. Nopco Base No. 1 (a 3-1 ratio mix of 'a 12 mol polyethylene oxide adduct of octyl phenol and 6 mol polyethylene oxide adduct of octyl phenol) and a percent active sodium petroleum sulfonate mixture can be conventionally employed. In addition to the above-mentioned ingredients optional additives, for instance, corrosion inhibiting agents, auxiliary emulsifying agents, coupling agents, antifoam agents, and deodorants can also be included in the novel compositions of the present invention. In use as a component of a soluble oil emulsion, the compositions are dispersed in about 1 to 200 or more parts of water, depending upon the particular application contemplated.

The following examples set out lubricating compositions in which'the active ingredients act as effective bacteriostatic agents. It is not intended that the present invention be limited to the compositions, portions, or lubricants set out below, but rather it is intended for all equivalents and variations obvious to those skilled in the art to be included within the scope of this specification and the.attached claims.

Example I To illustrate the use of 1,3-bis[3-(oxazolidinyl)] propanes in cutting oils, a 25 :1 water-cutting oil mixture Was prepared. The cutting o'il concentrate used was a proprietary cutting oil containing no bacteria inhibitors such as 4 that sold by Texaco Incorporated under the name of Soluble Oil TexacoC. To each of six one-gallon containers was added 1 liter of a water-cutting oil mixture.

Desired amounts of the 1,3-bis[3-(oxazolidinyl)]propane were added to the cutting oil mixture in five of the containers. No inhibitor was added to the other container which was used as a control. At the beginning of the experiment each unit was inoculated with 5 mls. of a heterogeneous bacteria culture which had grown for several years in a water-cutting oil mixture. Aeration and mixing were obtained by using an air lift to continually circulate the mixture. The test was continued for a period of six weeks and during the six weeks period, 5 mls. of bacteria culture were added at periodically weekly intervals.

The following table sets out'the results of the above tests.

Example II The following is a water emulsifiable cutting oil which is adequately protected by 1000 ppm. of l,3-bis[3-(oxazolidinyl) propane inhibitor:

. Percent by weight Light mineral oil Oleic acid 10 Example III The following is a stabilized steam cylinder oil which is adequately protected by 1000 ppm. of 1,3-bis[3-(oxazolidinyl) propane inhibitor:

Percent S.A.E. lubricating oil Oleic acid 10 Example IV The following is a core oil which is adequately protected by 1 000 p.p.m. of 1,3-bis[3-(oxazolidinyl) propane inhibitor:

Percent Crude tall oil 25 Fuel oil 35 Tall oil ester (glycol or glycerol) 40 Example V The following is a cutting oil which is adequately protected by 1000 ppm. of l,3-bis[3-(oxazolidinyl) propane inhibitor:

It is claimed: 1. A liquid petroleum lubricant composition consisting essentially of a petroleum hydrocarbon lubricant and a wherein R is selected from the group consisting of lower alkyl, lower hydroxyalkyl, and hydrogen and R is lower alkyl.

amount of a mineral lubricating oil base, an emulsifying agent in emulsifying amounts, and bacteria inhibiting amounts of a 1,3-bis[3-(oxazolidinyl)]nitropropane having the following formula:

wherein R is selected from the group consisting of lower alkyl, lower hydroxyalkyl, and hydrogen and R is lower alkyl.

2. A soluble oil composition comprising a major 3. The composition of claim 2 wherein the nitropropane is 2-nitro-2-methyl-1,3-bis[3-(oxazolidinyl) ]propane.

4. The composition of claim 2 wherein the nitropropane is 2-nitro12-methyl-1,3-bis[3-(4,4 dimethyloxazolidinyl) ]propane.

5. The composition of claim 2 wherein the nitropropane is 2-nitro-2-ethyl-1,3 bis[3 (4,4 dimet-hyloxazolidinyl) propane.

6. The composition of claim 2 wherein the nitropropane is 2-nitro-2-methyl-1,3-bis[3-( 4,4-dihydroxymethyloxazolidinyl) Jpropane.

7. The composition of claim 2 wherein the nitropropane is Z-nitro-Z-methyl 1,3 bis[3 (5 methyloxazolidinyl) ]propane.

References Cited by the Examiner UNITED STATES PATENTS 2,913,414 11/1959 Hodge 252-51.5 2,976,244 3/1961 Bennett 252-515 2,987,479 6/ 1961 Bennett 252-5 1 .5 3,033,785 5/ 1962 Bennett 252-51.5 X

DANIEL E. WYMAN, Primary Examiner.

P. P. GARVIN, Assistant Examiner. 

1. A LIQUID PETROLEUM LUBRICANT COMPOSITION CONSISTING ESSENTIALLY OF A PETROLEUM HYDROCARBON LUBRICANT AND A BACTERIA-INHIBITING AMOUND OF A 1,3-BIS(3-(OXAZOLIDINYL))NITROPROPANE HAVING THE FOLLOWING FORMULA: 